CN105449166A - Manufacturing method for negative electrode pole piece for sodium ion battery - Google Patents
Manufacturing method for negative electrode pole piece for sodium ion battery Download PDFInfo
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- CN105449166A CN105449166A CN201510801013.3A CN201510801013A CN105449166A CN 105449166 A CN105449166 A CN 105449166A CN 201510801013 A CN201510801013 A CN 201510801013A CN 105449166 A CN105449166 A CN 105449166A
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- ion battery
- sodium
- pole piece
- active material
- cathode pole
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000011149 active material Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011889 copper foil Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 17
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 229960001484 edetic acid Drugs 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 claims description 4
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- IFRDBGYJSLDMHQ-UHFFFAOYSA-J magnesium;disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Mg+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O IFRDBGYJSLDMHQ-UHFFFAOYSA-J 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000000840 electrochemical analysis Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- QEVZDLIWCQXMAY-UHFFFAOYSA-J magnesium;disodium;ethane-1,2-diamine;tetraacetate Chemical class [Na+].[Na+].[Mg+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCN QEVZDLIWCQXMAY-UHFFFAOYSA-J 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- -1 preferably Chemical compound 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a manufacturing method for a negative electrode pole piece for a sodium ion battery. The manufacturing method comprises the steps of uniformly grinding an active material, and performing vacuum drying to obtain the active material used for the negative electrode of the sodium ion battery; performing slurry mixing from the active material, a conductive agent and a binder based on proportion, and uniformly coating a current collector copper foil with the slurry, and then performing vacuum drying and tabletting to obtain the negative electrode pole piece for the sodium ion battery. Compared with the prior art, the manufacturing method provided by the invention is simple. An electrochemical test proves that the negative electrode pole piece is high in cycling stability, and relatively high in specific discharge capacity; the first time discharge capacity can reach 568mAh/g under the current density of 100mA/g; after the battery is circulated for 50 times, the discharge capacity still can be stabilized at 194mAh/g; and meanwhile, the manufacturing method is high in economic benefit and applicable to large-scale production.
Description
Technical field
The invention belongs to sodium-ion battery technical field, especially relate to a kind of manufacture method of sodium-ion battery cathode pole piece.
Background technology
Along with day by day highlighting of energy crisis, greatly developing novel energy-storing system becomes one of study hotspot of researcher instantly.New forms of energy are as the pillar of novel industry, and the development of various novel energy-storing system electronics receives the concern of numerous industry.From portable electric appts, cell phone, notebook computer, arrive power vehicle etc., people also become large to the demand of secondary cell thereupon.Traditional secondary cell specific energy is lower, cannot meet the demand of people, and therefore, the energy-storage system developing novel high-energy-density of future generation seems particularly important.
In the last few years, lithium ion battery technology obtained vigorous growth, and a large amount of lithium ion battery devices is also widely used.But, in lithium ion battery, lower as indispensable elemental lithium reserves abundance on earth.Along with the extensive use of lithium ion battery, the demand of elemental lithium also increases year by year.Therefore, it is also proposed higher requirement to exploitation exploitation lithium, meanwhile, this also will play inhibitory action to a certain extent to large-scale production rechargeable lithium ion batteries energy storage device.Sodium element, belongs to same major element with elemental lithium in the periodic table of elements.The rich reserves of sodium element not only in the earth's crust, reserves are in the seawater also quite large.Be similar in electrochemical reaction medium power scholarship and moral conduct, therefore our chargeable sodium-ion battery that sodium element can be replaced elemental lithium mass production of cheap be easy to get.
(the XuehangWu such as WuXuehang, WenweiWun, KaituoWang, WenChenandDanHe. " Synthesisandelectrochemicalperformanceofflower-likeMnCo2 O4asananodematerialforsodiumionbatteries " MaterLett., 2015,147,85-87.) report a kind of negative material of cobalt acid manganese material as sodium-ion battery being similar to colored shape, under 50mA/g current density, after circulation is enclosed in discharge and recharge 40, specific discharge capacity remains on 244mAh/g.Although the electrical property that this negative material obtains has certain advantage, but metal oxide de-/embedding sodium ion time, there is huge change in the volume of active material, until active material configuration subsides, departs from collector, and causes the decay of chemical property because of convergent-divergent.
Prabakar, (the Prabakar such as S.J.Richard, S.J.Richard, Jeong, JaehyangandPyo, Myoungho. " Nanoporoushardcarbonanodesforimprovedelectrochemicalperf ormanceinsodiumionbatteries " ElectrochimicaActa, 2015, 161, 23-31.) report and utilize sucrose to prepare a kind of nano-pore hard carbon, and using the negative material of this carbon as sodium-ion battery, under the current density of 20mA/g, first discharge specific capacity is 251mAh/g, charge and discharge cycles is after 100 weeks, specific discharge capacity remains on 213mAh/g.But the preparation method of this active material is complicated, and technique is tediously long, is difficult to realize suitability for industrialized production.
Summary of the invention
Object of the present invention is exactly provide the manufacture method of the sodium-ion battery cathode pole piece that a kind of specific discharge capacity is higher, stable cycle performance, result are reproducible to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A manufacture method for sodium-ion battery cathode pole piece, adopts following steps:
(1) active material ground evenly and carry out vacuumize, obtaining the active material for sodium-ion battery negative pole;
(2) be evenly applied on copper foil of affluxion body after active material, conductive agent, binding agent being sized mixing in proportion, vacuumize, compressing tablet, prepare sodium-ion battery cathode pole piece.
Active material described in step (1) is selected from the one in class chelates such as ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, Ferric Sodium Edetate or ethylenediamine tetraacetic acid disodium magnesium salt, preferably, ethylenediamine tetra-acetic acid can be adopted.Grind uniform active material at 60-150 DEG C of vacuumize 6-10h.
Conductive agent described in step (2) is one or more in superconduction carbon black, electrically conductive graphite or Ketjen black; Binding agent is one or more in Kynoar, carboxymethyl cellulose or sodium alginate.The mass ratio of active material, conductive agent and binding agent is (4-8): (5-1): 1.Middle vacuumize temperature is 60-150 DEG C, and the time is 5-12h, and pressure is 1-6Pa.
Sodium-ion battery cathode pole piece making obtained is as test electrode, and sodium metal, as to electrode, is assembled into CR2016 type button cell, and its septation is for commonly using glass fibre membrane in this field, and electrolyte is: 1MNaClO
4/ EC:DEC (1:1)+5wt%FEC, test charging and discharging currents density is 100mA/g.
Compared with prior art, the present invention is using class chelates such as ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, Ferric Sodium Edetate, ethylenediamine tetraacetic acid disodium magnesium salts as sodium-ion battery negative pole active material.Above-mentioned substance is of many uses, cheap and easy to get.In charge and discharge process, sodium ion can be free to replace H or metal ions M on the COOH of this kind of chelate (M) group, and realize embedding freely and deviating from, as the negative active core-shell material of sodium-ion battery, economic benefit is given prominence to, and under the current density of 100mA/g, first discharge specific capacity is 568mAh/g, after 50 circulations, specific discharge capacity still remains on more than 194mAh/g, has good electrochemical cycle stability.The invention provides a kind of active material and the cathode pole piece preparation that can be used for sodium-ion battery negative pole, method is simple, is easy to operation, and technological process is succinct, is applicable to large-scale production.
Accompanying drawing explanation
The SEM figure of the sodium-ion battery cathode pole piece of Fig. 1 prepared by embodiment 1;
Fig. 2 is the isothermal nitrogen adsorption desorption curve chart of the sodium-ion battery negative pole active material that embodiment 2 uses;
Fig. 3 is that sodium-ion battery cathode pole piece prepared by embodiment 2 is assembled into the first charge-discharge curve chart of battery;
Fig. 4 is that sodium-ion battery cathode pole piece prepared by embodiment 2 is assembled into the recycle ratio Capacity Plan of battery;
Fig. 5 is that sodium-ion battery cathode pole piece prepared by embodiment 3 is assembled into the recycle ratio Capacity Plan of battery.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Active material ethylenediamine tetra-acetic acid is positioned in vacuum drying chamber, after 60 DEG C of dry 10h, as sodium-ion battery negative active core-shell material.By this negative material, conductive agent superconduction carbon black (SP), binding agent Kynoar (PVDF) in mass ratio 6:3:1 mix, with 1-METHYLPYRROLIDONE (NMP) for solvent, evenly be applied on copper foil of affluxion body after sizing mixing, be positioned over vacuum drying chamber, at 60 DEG C after dry 12h, adopt 3Pa pressure compressing tablet, obtain sodium-ion battery cathode pole piece, Fig. 1 is the SEM figure of sodium-ion battery cathode pole piece.As can be seen from the figure, the surface ratio of electrode slice is comparatively even, can be found out by partial enlarged drawing, and it is relatively more even that active material disperses, and particle diameter is approximately between 50-100nm.
Embodiment 2
Active material disodium ethylene diamine tetraacetate is positioned in vacuum drying chamber, after 150 DEG C of dry 6h, as sodium-ion battery negative active core-shell material.By this negative material, electrically conductive graphite, binding agent sodium alginate (SA) in mass ratio 8:1:1 mix, take distilled water as solvent, evenly be applied on copper foil of affluxion body after sizing mixing, be positioned over vacuum drying chamber, at 150 DEG C after dry 5h, adopt 4Pa pressure compressing tablet, obtain sodium-ion battery cathode pole piece, Fig. 2,3,4 is respectively the isothermal nitrogen adsorption desorption curve chart of sodium-ion battery negative pole active material, sodium-ion battery cathode pole piece is assembled into battery first charge-discharge curve chart and recycle ratio Capacity Plan.As can be seen from the isothermal nitrogen adsorption desorption curve of Fig. 2 active material disodium ethylene diamine tetraacetate, middle nip territory (0.3-0.9), there is an obvious hysteresis loop in curve, illustrates that this kind of material has certain meso-hole structure; Higher-pressure region (0.9-1.0) adsorption curve has an obvious nose-up tendency, and adsorbance increases suddenly, shows to there is a large amount of fissure holes in this material.The existence of hole, can better wetting activity material, simultaneously also for the transmission of sodium ion provides a large amount of passages.Fig. 3 is the first charge-discharge curve chart of this cathode pole piece assembling sodium-ion battery, and first discharge specific capacity reaches 464mAh/g, and electric discharge occurs that the some position that turnover is is respectively about 1.0V and 0.75V.Fig. 4 is the charge and discharge cycles figure of battery.Under charging and discharging currents density is 100mA/g, battery is after electrochemical activation process, the specific discharge capacity of the 2nd week decays to 169mAh/g, in ensuing circulation, this battery shows good cyclical stability, after 50th week charge and discharge cycles, specific discharge capacity is still higher remains on 155mAh/g and efficiency for charge-discharge (=specific discharge capacity/charge specific capacity × 100%) remains on about 100% substantially.
Embodiment 3
Active material tetrasodium ethylenediamine tetraacetate is positioned in vacuum drying chamber, after 80 DEG C of dry 9h, as sodium-ion battery negative active core-shell material.By this negative material, Ketjen black, binding agent carboxymethyl cellulose (CMC) in mass ratio 7:2:1 mix, take distilled water as solvent, evenly be applied on copper foil of affluxion body after sizing mixing, be positioned over vacuum drying chamber, at 80 DEG C after dry 10h, adopt 2Pa pressure compressing tablet, obtain sodium-ion battery cathode pole piece, be assembled into battery, the recycle ratio capacity of this battery as shown in Figure 5.Fig. 5 is the charge and discharge cycles figure of battery.Under charging and discharging currents density is 100mA/g, first discharge specific capacity is up to 568mAh/g, after the electrochemical activation process of a week, the specific discharge capacity of the 2nd week reduces to 206mAh/g, in ensuing circulation, this battery shows good cyclical stability, and after the 50th week charge and discharge cycles, specific discharge capacity is still higher remains on 194mAh/g and efficiency for charge-discharge remains on about 100% substantially.
Embodiment 4
Active material Ferric Sodium Edetate is positioned in vacuum drying chamber, after 120 DEG C of dry 7h, as sodium-ion battery negative active core-shell material.By this negative material, conductive agent superconduction carbon black (SP), binding agent Kynoar (PVDF) in mass ratio 4:5:1 mix, with 1-METHYLPYRROLIDONE (NMP) for solvent, evenly be applied on copper foil of affluxion body after sizing mixing, be positioned over vacuum drying chamber, at 120 DEG C after dry 8h, adopt 1Pa pressure compressing tablet, obtain sodium-ion battery cathode pole piece.
Embodiment 5
Active material ethylenediamine tetraacetic acid disodium magnesium salt is positioned in vacuum drying chamber, after 100 DEG C of dry 8h, as sodium-ion battery negative active core-shell material.By this negative material, conductive agent superconduction carbon black (SP), binding agent sodium alginate (SA) in mass ratio 5:4:1 mix, take distilled water as solvent, evenly be applied on copper foil of affluxion body after sizing mixing, be positioned over vacuum drying chamber, at 70 DEG C after dry 11h, adopt 6Pa pressure compressing tablet, obtain sodium-ion battery cathode pole piece.
This experiment is assembled into CR2016 type button cell respectively to embodiment 1-5 gained sodium-ion battery cathode pole piece.This button cell is gained in each embodiment by cathode pole piece, is formed electrode metal sodium, fibreglass diaphragm, electrolyte and shell.Wherein electrolyte is: 1MNaClO
4/ EC:DEC (1:1 volume ratio, EC: ethylene carbonate, DEC: diethyl carbonate)+5wt%FEC (FEC: fluorinated ethylene carbonate).
LAND test macro is adopted under room temperature environment, to carry out electric performance test to the battery prepared by embodiment 1-5 gained sodium-ion battery negative pole respectively.Wherein, before testing sodium-ion battery is positioned in the environment of 40 DEG C and leaves standstill 2h; During test, charging and discharging currents density is 100mA/g, and discharge and recharge cut-ff voltage is 0.01-3V (vs.Na/Na
+).
Claims (8)
1. a manufacture method for sodium-ion battery cathode pole piece, is characterized in that, the method adopts following steps:
(1) active material ground evenly and carry out vacuumize, obtaining the active material for sodium-ion battery negative pole;
(2) be evenly applied on copper foil of affluxion body after active material, conductive agent, binding agent being sized mixing in proportion, vacuumize, compressing tablet, prepare sodium-ion battery cathode pole piece.
2. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1, it is characterized in that, the active material described in step (1) is selected from one or more of ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, Ferric Sodium Edetate or ethylenediamine tetraacetic acid disodium magnesium salt.
3. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1, is characterized in that, the preferred ethylenediamine tetra-acetic acid of active material described in step (1).
4. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1, is characterized in that, in step (1), the uniform active material of grinding is at 60-150 DEG C of vacuumize 6-10h.
5. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1, is characterized in that, the conductive agent described in step (2) is one or more in superconduction carbon black, electrically conductive graphite or Ketjen black.
6. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1, is characterized in that, the binding agent described in step (2) is one or more in Kynoar, carboxymethyl cellulose or sodium alginate.
7. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1 or 5 or 6, is characterized in that, in step (2), the mass ratio of active material, conductive agent and binding agent is (4-8): (5-1): 1.
8. the manufacture method of a kind of sodium-ion battery cathode pole piece according to claim 1, is characterized in that, in step (2), vacuumize pressure is 1-6Pa, and temperature is 60-150 DEG C, and the time is 5-12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510801013.3A CN105449166B (en) | 2015-11-19 | 2015-11-19 | A kind of preparation method of sodium-ion battery cathode pole piece |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510801013.3A CN105449166B (en) | 2015-11-19 | 2015-11-19 | A kind of preparation method of sodium-ion battery cathode pole piece |
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| Publication Number | Publication Date |
|---|---|
| CN105449166A true CN105449166A (en) | 2016-03-30 |
| CN105449166B CN105449166B (en) | 2018-02-02 |
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Cited By (7)
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| CN106099064A (en) * | 2016-08-03 | 2016-11-09 | 常州大学 | A kind of SnS2the preparation method of/CNTs composite nano materials and the application as anode material of lithium-ion battery thereof |
| CN106848242A (en) * | 2017-02-27 | 2017-06-13 | 苏州大学 | A kind of organic lithium storage materials of high power capacity and its application |
| CN108172786A (en) * | 2017-12-22 | 2018-06-15 | 上海交通大学 | A kind of lithium cell cathode material based on fused ring compound and preparation method thereof |
| CN108269990A (en) * | 2018-03-06 | 2018-07-10 | 广东工业大学 | A kind of anode material of lithium-ion battery and preparation method thereof and battery |
| CN109565037A (en) * | 2016-07-18 | 2019-04-02 | 宁德时代新能源科技股份有限公司 | Sodium-ion battery pole piece, preparation method and the sodium-ion battery containing the pole piece |
| CN115513526A (en) * | 2022-10-31 | 2022-12-23 | 东莞市创明电池技术有限公司 | Electrolyte and battery |
| CN116404117A (en) * | 2023-06-07 | 2023-07-07 | 四川富临新能源科技有限公司 | Method for improving capacity of sodium ion positive electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109565037A (en) * | 2016-07-18 | 2019-04-02 | 宁德时代新能源科技股份有限公司 | Sodium-ion battery pole piece, preparation method and the sodium-ion battery containing the pole piece |
| CN109565037B (en) * | 2016-07-18 | 2022-03-08 | 宁德时代新能源科技股份有限公司 | Sodium ion battery pole piece, preparation method thereof and sodium ion battery containing pole piece |
| CN106099064A (en) * | 2016-08-03 | 2016-11-09 | 常州大学 | A kind of SnS2the preparation method of/CNTs composite nano materials and the application as anode material of lithium-ion battery thereof |
| CN106099064B (en) * | 2016-08-03 | 2019-12-06 | 常州大学 | Preparation method of SnS2/CNTs composite nano material and application of composite nano material as negative electrode material of sodium-ion battery |
| CN106848242A (en) * | 2017-02-27 | 2017-06-13 | 苏州大学 | A kind of organic lithium storage materials of high power capacity and its application |
| CN108172786A (en) * | 2017-12-22 | 2018-06-15 | 上海交通大学 | A kind of lithium cell cathode material based on fused ring compound and preparation method thereof |
| CN108172786B (en) * | 2017-12-22 | 2020-04-03 | 上海交通大学 | Lithium battery negative electrode material based on condensed ring compound and preparation method thereof |
| CN108269990A (en) * | 2018-03-06 | 2018-07-10 | 广东工业大学 | A kind of anode material of lithium-ion battery and preparation method thereof and battery |
| CN115513526A (en) * | 2022-10-31 | 2022-12-23 | 东莞市创明电池技术有限公司 | Electrolyte and battery |
| CN116404117A (en) * | 2023-06-07 | 2023-07-07 | 四川富临新能源科技有限公司 | Method for improving capacity of sodium ion positive electrode material |
| CN116404117B (en) * | 2023-06-07 | 2023-08-11 | 四川富临新能源科技有限公司 | Method for improving capacity of sodium ion positive electrode material |
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